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Stepwise recycling of valuable metals from spent

lithium-ion batteries based on in situ thermal
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Cite this: DOI: 10.1039/d3gc01673k

reduction and ultrasonic-assisted water leaching
Wei Ding, a,b Shenxu Bao, *a,b,f Yimin Zhang,c Liuyi Ren,a,b,f Chunfu Xin,a,b
Bo Chen,a,b Bo Liu,a,b Junhui Xiao d and Xiaochuan Houe

Received 18th May 2023,
Accepted 26th July 2023
DOI: 10.1039/d3gc01673k
rsc.li/greenchem
Recycling spent lithium-ion batteries (LIBs) is essential for sustainable resource utilization and environ-
mental conservation. In this research, we have achieved simultaneous removal of organic matter, dis-
sociation of electrode material, and reduction of high valence transition metal through the process of
in situ thermal reduction, which are key points for the hierarchical selective recovery of valuable metals.
The thermal reduction mechanism and phase transition behavior of mixed electrode materials were also
evaluated in the meantime. It is found that the spent cathode materials were decomposed and synchro-
nously reduced to the form of MnO, NiO, Ni, Co, LiF, Li2O, LiAlO2, and Li2CO3 through in situ thermal
reduction during roasting at 650 °C for 1 h. The maximum leaching efficiency of Li under conventional
water-leaching conditions was found to be 85.66%. Ultrasonic-assisted leaching has been shown to
cause ultrasonic cavitation effects in the leaching process, promoting the dissolution and desorption of
LiF, Li2CO3, and Li2O through mechanical action and thermal impacts at the solid–liquid interface,
increasing the Li leaching efficiency to 98.68% (more than a 13% increase). The recovered leaching solu-
tion was evaporated and crystallized to obtain high-purity Li2CO3 (≥99.5%). Subsequently, the transition
metals were separated from aluminum, copper, and graphite by wet magnetic separation. The leaching of
high-value metals Ni, Mn, and Co from magnetically enriched products using sulfuric acid at room temp-
erature without a reducing agent has greatly simplified the subsequent transition metal separation
process. This study presents a potential avenue for the efficient and environmentally-friendly recovery of
valuable metals from mixed electrode materials of spent LIBs.

1. Introduction available, LIBs are widespread application in electronic

Lithium-ion batteries (LIBs) employ lithium metal or lithium
alloy as the cathode material and possess rechargeable capa-
bilities. They offer several advantages, including high energy
density, small size, lightweight design, and fast charging capa-
bilities.1 As one of the most advanced rechargeable batteries
a
School of Resources and Environmental Engineering, Wuhan University of
Technology, Wuhan 430070, China. E-mail: sxbao@whut.edu.cn
b
Hubei Key Laboratory of Mineral Resources Processing and Environment,
Wuhan 430070, China
c
State Environmental Protection Key Laboratory of Mineral Metallurgical Resources
Utilization and Pollution Control, Wuhan University of Science and Technology,
Wuhan 430081, China
d
School of Environment and Resource, Southwest University of Science and
Technology, Mianyang 621010, China
e
Zhejiang New Era Zhongneng Recycling Technology Co., Ltd, Shaoxing 312000,
China
f
Shaoxing Institute for Advanced Research, Wuhan University of Technology,
Shaoxing 312000, China
devices, electric cars, and as reserve power sources.2 In 2022,
the new energy vehicle markets in China and Europe per-
formed exceptionally well. The trend towards green and low-
carbon development has led to significant demand for LIBs in
China’s power system storage and European and American
family storage markets. According to statistics, China’s ship-
ment of LIBs is expected to exceed 1 TW h in 2023, which rep-
resents a year-on-year increase of 80%. Specifically, power
battery shipments will reach 800 GW h, while storage battery
shipments will reach 300 GW h.3
LIBs have a limited lifespan of approximately 5 years, as
their capacity diminishes to below 80% after roughly 1000
cycles of charging and discharging. The global market for re-
cycling LIBs reached 111 783 tons in 2018 and is projected to
reach 641 595 tons by 2025, exhibiting a compound annual
growth rate of 26.57% during the forecast period.4
Consequently, there is a significant quantity of retired LIBs
that must be appropriately managed to prevent environmental
contamination and safety hazards.5 Nickel–cobalt–copper is

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considered the cornerstone of the energy revolution, providing
feedstock for new energy vehicles and energy storage equip-
ment. It has been designated as a critical mineral by numerous
countries and regions. Spent LIBs are a potential source of
valuable metals, including cobalt, nickel, and lithium.6
Extracting metals from spent LIBs with high metal content
and few impurities is comparatively easier than extracting
metals from raw resources such as natural minerals or brine
with low metal content.7 Additionally, graphite powder in the
negative material of LIBs is prone to producing dust pollution
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due to its small particles.8 It is critical to appropriately recycle
spent LIBs to mitigate environmental pollution and safety
risks associated with toxic gases such as HF produced by cor-
rosive solutes like lithium hexafluorophosphate.9 In summary,
comprehensive spent LIBs are essential to reduce environ-
mental pollution and safety hazards while reclaiming valuable
metals.
Currently, the primary focus of spent LIBs recycling is to
extract high-value metals like lithium, cobalt, and nickel from
the positive electrode materials. Hydrometallurgical or pyro-
metallurgical technologies are typically employed depending
on the target metal to be separated. However, to prioritize the
recovery of Li from spent LIBs, alternative leaching methods
have been developed using Na2S2O8 oxidation,10 oxalic
acid,11,12 tartaric acid,13 and phosphoric acid.14,15
Unfortunately, these leaching agents are expensive, slow the
leaching kinetics, and require complex residue treatment,
which currently hinders improvement.16 Once the target
metals (Co, Ni, Mn, and Li) are recovered from spent LIBs,
both classical and newly developed metallurgical processes
face the challenge of high lithium loss. To combat this bottle-
neck, selective extraction technology based on a combination
of pyrometallurgy and hydrometallurgy has become a popular
research topic and development direction for retiring LIBs
both domestically and abroad.16–18 Previous studies have
demonstrated that combined methods like reduction roasting
with nitrate, sulfate, and carbon powders, followed by a water-
leaching process, can effectively extract Li from spent LIBs.19
Although reduction roasting with nitrate or sulfate can
efficiently extract valuable metals, particularly Li, from spent
LIBs, resulting in a significant reduction in energy con-
sumption and production costs, there are two drawbacks to
consider. Firstly, the use of sulfate as an additive intro-
duces impurity ions such as Na and K, which reduces
product purity and increases the cost of impurity removal.
Secondly, the roasting process of sulfate and nitrate gener-
ates SO 2, NO, and NO2, which poses serious environmental
problems requiring resolution before this method is
applied on an industrial scale. Additionally, the roasting
kinetics of this method is relatively slow, and the reagent
cost is high.9,20,21
Carbothermic reduction roasting (CTR) is considered a
promising technique for roasting spent LIBs due to its
inherent advantages, such as relatively low treatment tempera-
ture, minimal usage of chemical reagents, and simple oper-
ation.22 Recent research on the priority recovery of Li from
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spent LIBs using CTR-water leaching has focused on roasting
cathode materials with graphite recovered from anode
materials. This implies that the anode and cathode materials
must be separated during pretreatment. However, since the
cathode material was wrapped by organic binders, carbon
black, and aluminum foils, it is difficult to separate the elec-
trode material from aluminum foils only by mechanical crush-
ing, while fine electrode particles easily adhere to each other.
This results in the process of separating the anode and
cathode after automatic crushing is time-consuming and
complex.23 Simultaneously, the reducibility of organic binder,
carbon black, and aluminum foil in the mixed electrode
material creates favorable conditions for the in situ thermal
reduction of the positive electrode material. There have been
scarcely reports on the recovery of lithium by the CTR-water
leaching method from the electrode mixture produced by
direct crushing and dismantling of spent LIBs. Therefore,
studying the in situ reduction roasting behavior and reaction
mechanism during the CTR of electrode mixture materials is
crucial. This will facilitate the directional enrichment of target
metals during the in situ thermal reduction process, optimize
reactor design, and potentially streamline spent LIBs recovery
procedures.
It is noteworthy that relevant research has indicated that a
significant proportion of carbonaceous materials (graphite
etc.) will inevitably remain in the roasted products following
CTR.24 These materials can easily absorb lithium ions and
inhibit the selective recovery of lithium carbonate in the water-
leaching solution. Ultrasonic-assisted leaching has been
shown to cause ultrasonic cavitation effects in the leaching
process, promoting the dissolution and desorption of lithium
carbonate through mechanical action and thermal impacts at
the solid–liquid interface.25–28 Makuza et al.24 reported the
selective extraction of Li by dry grinding-carbonation ultra-
sonic-assisted water leaching of carbothermal reduction spent
LIBs, but the leaching time was up to 3 hours due to the low
ultrasonic power (200 W). To reflect the industrial application
advantages of ultrasonic-assisted leaching technology in the
selective recovery of lithium from spent LIBs, a high-power
ultrasonic generator was utilized for ultrasonic agitation
instead of an ultrasonic cleaning machine.
In this study, we aimed to develop a process that could
achieve enhanced selectivity, efficiency, and environmental
sustainability in the recovery of valuable metals from spent
LIBs mixed electrode materials. The thermodynamic feasibility
of the in situ reduction process, the phase transitions of Li, Ni,
Co, and Mn, and the leaching behavior of Li under various
roasting conditions were comprehensively investigated.
Additionally, it investigated the leaching behavior of Li with
different operating parameters and the mechanisms that
enhance Li leaching under ultrasonic-assisted leaching.
Finally, pure lithium carbonate products were obtained from
the water-leaching solution, and the subsequent separation
process of transition metals was greatly simplified by selec-
tively separating Ni, Co, and Mn from the water-leaching
residue via magnetic separation.
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2. Experimental
2.1. Materials
The spent NMC LIBs used in this study were provided as a
shredded ‘black mass’ powder (mixture of cathode materials
and anode materials) from a recycling company in China,
Zhejiang New Era Zhongneng Recycling Technology Co., Ltd.
The elemental composition of the spent LIBs mixed electrode
materials is shown in Table 1. The sulfuric acid (H2SO4,
95–98%) was obtained from Sinopharm Chemical Reagent Co.,
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Ltd, China. For all experiments, solutions were prepared using
ultrapure water (Milli-Q, Millipore).
2.2. Experimental procedure
A combined process was used to achieve the stepwise recovery
of valuable metals, including in situ thermal reduction, ultra-
sonic-assisted water leaching, wet magnetic separation, and
sulfuric acid leaching. The flow chart for disposing of spent
LIBs is displayed in Fig. 1. Firstly, discharge treatment was
conducted prior to the crushing process to avoid an explosion
or fire. Discharged batteries were disassembled and sorted by
size and quality to generate mixed electrode materials.
Afterward, the spent electrode material was decomposition by
in situ thermal reduction, transforming it into water-soluble
lithium compounds and transition metal elements or com-
pounds. Selective leaching of lithium from the roasted product
was then conducted using ultrasonic-assisted water leaching.
Subsequently, a solution containing Co2+–Ni2+–Mn2+ was
formed via a magnetic separation-sulfuric acid leaching
process, with most of the graphite, copper, and aluminum
retained in the tailings of magnetic separation.
2.2.1. In situ thermal reduction. To investigate the effect of
different roasting conditions on the phase transformation of
mixed electrode materials and Li leaching efficiency (LLi),
the tube furnace was first heated to a designed temperature
gradually. Then the mixed electrode materials (5 g) were
placed in an argon-filled tube furnace (OTF-1200X, China)
and roasted for a specific time under an argon atmosphere.
After cooling naturally to below 100 °C, the argon was
turned off and removed the sample. The roasting tempera-
ture was varied between 500 °C and 700 °C, and the roasting
time was varied between 0.5 h and 2.5 h. The tail gas, which
contains toxic gases such as CH3CHO, CO2, and HF, was cap-
tured and treated through absorption in a wash bottle con-
taining a NaOH solution. To ensure consistency in the ana-
lysis, conventional water-leaching conditions (a liquid–solid
ratio (L/S ratio) of 15 mL g−1, leaching at 25 °C for 2 h, and
magnetic stirring of 200 rpm) were used across all
experiments.
Table 1 Elemental composition of spent LIBs mixed electrode materials
Elements C Li Ni
Content, wt% 42.30 3.23 11.07
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Fig. 1 The flow chart for disposing of spent LIBs.
2.2.2. Ultrasonic-assisted water leaching. To extract lithium
from roasted products, 10 g of the products were mixed with
ultrapure water at different L/S ratios in a double-layer glass
reactor. Ultrasonic-assisted water leaching was then performed
using an ultrasonic device (VS-SHX-1000W, China), and the
impacts of operating parameters on LLi were investigated,
including ultrasonic power (150, 300, 450, 600, 750 W), ultra-
sonic time (2, 5, 10, 20, 30 min), L/S ratio (5 : 1, 10 : 1, 15 : 1,
20 : 1, 25 : 1 mL g−1), and leaching temperature (20, 25, 30, 35,
40 °C). The resulting slurry was filtered using vacuum fil-
tration, and the residue left after filtration was dried at 105 °C.
2.2.3. Wet magnetic separation-sulfuric acid leaching.
The water-leaching residue was separated using an
XCGS-13 magnetic tube at 1100 Gauss magnetic intensity,
resulting in the production of magnetic products and non-
magnetic tailings. The magnetic products were then subjected
to further leaching using 3 M sulfuric acid. The leaching
process was conducted in a 100 mL glass beaker with an L/S
ratio of 5 mL g−1 under magnetic stirring at 200 rpm and
30 °C. The leaching time was varied, with durations of 1, 2,
and 3 h.
2.3. Characterization and analysis
The metal element composition of the materials and solution
was determined using inductively coupled plasma-optical
emission spectrometry (ICP-OES, Prodigy 7, Leemanlabs, USA).
The carbon content of the solid samples was measured using
an element analyzer (EA, multi EA 4000, Germany). X-ray diffr-
action (XRD, Panaco, Netherlands; Cu, X Pert pro, the testing
angel (2θ) range of 10°–70° and the scanning rate of 10°
min−1) was used to characterize all crystal materials. The par-
ticle size distribution of the mixed electrode material was
determined by the Mastersizer 2000 Particle Size (Malvern,
UK). Scanning electronic microscopy (SEM, Sigma300,
Co Mn Cu Al Fe
6.19 12.81 7.63 7.01 2.48
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Germany) equipped with an energy-dispersive X-ray analyzer
(EDX, EDAX Inc., USA) was used to examine the microstructure
and element distribution of samples. The SEM measurement
involves raster scanning the samples from top to bottom, and
the energy of the electron-focused beam was from 15 kV to 30
kV. The chemical states of elements in the measured samples
were identified using X-ray photoelectron microscopy (XPS,
Thermo Fisher Scientific ESCALAB 250Xi) equipped with a
monochromatic Al Kα X-ray source. The C 1s spectrum peak
(284.8 eV) was used for the calibration. The hysteresis loop of
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samples was tested using a Vibrating Sample Magnetometer
(VSM, Lake Shore7404, USA). Additionally, time-of-flight sec-
ondary ion mass spectrometry (TOF-SIMS) was acquired using
a PHI NanoTOFII instrument (TOF-SIMS 5 iontof, IONTOF,
Germany), which allowed for the acquisition of an iconic
image of the solid sample elements and corresponding depth
profiles beneath the surface films. High-mass resolution spec-
troscopy was conducted using a 30 keV Bi3+ ion source. A
raster size of 500 μm × 500 μm and a mass range of 1–1850 μ
were utilized for high spatial resolution imaging. The spot size
of the primary ion beam was approximately 200 nm.
The leaching efficiencies of valuable metals (Li, %) and wet
magnetic recovery efficiency (R, %) were determined using the
following formulas:
ci  vi
Li ¼  100%
m0  ω0
mr  ωr
R¼  100%
m0  ω0
where ci (g L−1) is the metal elements content in the solution,
vi (L) is the volume of the leaching solution, m0 (g) and mr (g)
are the mass of the raw materials and final products, respect-
ively; ω0 (g) and ωr (g) are the content of metal elements in
raw materials and final products, respectively. All experiments
Fig. 2 (a) XRD pattern, (b) size distributions, (c) different particle sizes metal elements content variation, and (d) SEM-EDS analysis of the spent LIBs.
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were carried out at least three times to ensure the accuracy of
the results.
3. Results and discussion
3.1. Characterization analysis of spent LIBs
As shown in Fig. 2a, the mixed electrode materials are predo-
minantly composed of cathode material, graphite, copper foil,
and aluminum foil. Particle size analysis indicates that 90% of
the samples have a size distribution below 158.49 μm, with
particle sizes ranging from 30 to 150 μm accounting for the
majority (Fig. 2b). The content of metal element components
in mixed electrode materials of different particle sizes is dis-
played in Fig. 2c. Notably, Cu and Al content is significantly
higher in coarse-grade components, while more valuable
metals (Co, Ni, and Mn) are concentrated in finer particles.
Furthermore, as the particle size decreases, the proportion of
cathode material gradually increases. SEM-EDS analysis results
depicted in Fig. 2d show that most of the cathode material
consists of relatively regular blocky particles, with organic
binder remaining on the surface. The surface of these particles
displays the uniform distribution of Ni, Co, Mn, and O
elements. However, multiple charge and discharge cycles
cause damage to the structure of some cathode materials,
ð1Þ resulting in broken hemispherical particles and irregular
small particles. Aluminum primarily exists in the form of
large, irregular blocks.
ð2Þ
3.2. In situ thermal reduction
3.2.1. Theoretical feasibility and thermal analysis. In situ
thermal reduction of mixed electrode materials involves the
decomposition of cathode material and various reduction reac-
tions.29 A theoretical thermodynamic analysis of this process
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would be valuable in guiding the experimental design and
aiding in the interpretation of results. Previous research uti-
lized HSC Chemistry to perform thermodynamic calcu-
lations, which identified that carbon powder could trigger
carbothermal reduction of LiNixCoyMnzO2 at temperatures
between 400 °C and 700 °C.30–32 This information provides
important insight into the mechanisms underlying in situ
thermal reduction and can inform future experimental
endeavors aimed at optimizing reduction conditions and
outcomes.
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To investigate the variation of phase and existing forms of
elements Li, Ni, Co, and Mn in the process of in situ thermal
reduction, the “Predom module” of FactSage 7.0 software with
the database FactPS was used to plot the thermodynamic pre-
dominance area diagrams of Li–TM–C–O system at different
temperatures. Based on related research, roasting temperatures
of 550 °C, 600 °C, and 650 °C were selected as the temperature
conditions for the thermodynamic predominance area dia-
grams of the Li–TM–C–O system. The calculated distribution
of the reduction roasting reaction products is shown in Fig. 3,
where PCO and PO2 are the equilibrium partial pressures of CO
and O2 in the gas phase, and P° is the standard atmospheric
pressure.
The thermodynamic predominance area diagrams of the
Li–Co–C–O system at various temperatures are presented in
Fig. 3(A–C). As the temperature increases from 550 °C to
Fig. 3 Thermodynamic predominance area diagrams of Li–TM–C–O system (Li–Co–C–O, A-550 °C, B-600 °C, C-650 °C; Li–Ni–C–O, D-550 °C,
E-600 °C, F-650 °C; Li–Mn–C–O, G-550 °C, H-600 °C, I-650 °C).
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650 °C, the stable region area of Li2O, CoO, and Co continu-
ously expands, while the stable region area of Li2CO3 gradually
shrinks. These results suggest that an appropriate roasting
temperature is crucial for the formation of Li2CO3 before
650 °C. Increasing the roasting temperature beyond this point
has an inhibitory effect on the formation of Li2CO3, but it
proves beneficial for the reduction of Co high-valent oxide.
The primary roasted products in the range of 550 °C–650 °C
consist of Li2CO3, CoO, Co3O4, and Co.
From Fig. 3(D–F), based on the information provided, it can
be inferred that as the roasting temperature increases, the area
of the thermodynamically stable region for Li2CO3 decreases.
Meanwhile, the stable regions of Ni and NiO shift to the right,
indicating that the difficulty of forming Li2CO3 increases and
the generation trend of Ni becomes stronger. This is likely
due to the fact that the reduction of nickel oxides depends on
both the roasting temperature and CO partial pressure.
Additionally, the roasting temperature and partial pressure of
CO and O2 are both factors that affect the formation of Li2O
from Li2CO3. At higher roasting temperatures, part of the Li2O
produced may combine with Ni or NiO, which could decrease
the amount of Li that leaches out during the water-leaching
process. It seems that the mass fraction of Ni in the reduction
products gradually increases as the roasting temperature
increases, suggesting that higher temperatures favor the for-
mation of Ni.
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It can be inferred that during the process of roasting in a
reduction atmosphere, the reduction path of Mn high-valent
oxide may be MnO2–Mn2O3–Mn3O4–MnO, as shown in Fig. 3
(G–I). Additionally, increasing the CO partial pressure is con-
ducive to the formation of MnO. Comparing the thermo-
dynamic predominance area diagrams at 600 °C and 650 °C, it
appears that increasing the roasting temperature leads to the
stable region of Li2CO3 + MnO and Li2CO3 + Mn3O4 moving
up. This, in turn, increases the formation trend of composite
oxide Li2O + MnO, which is not conducive to the production of
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Li2CO3. The leaching efficiency of lithium may be reduced.
On the whole, these findings suggest that careful control of
roasting temperature and gas composition is crucial for achiev-
ing the desired product composition and leaching efficiency. In
particular, maintaining a suitable roasting temperature and CO
partial pressure may be important for promoting the formation
of Li2CO3 while minimizing the formation of composite oxides.
3.2.2. Effect of roasting temperature. To explore the in situ
thermal reduction behavior of mixed electrode materials and
the effects of different roasting temperatures on valuable
metals’ phase transformation, microstructure, and leaching
efficiency of lithium. The phase characteristics of the mixed
electrode materials were analyzed in conjunction with the
roasted products at varying temperatures, as illustrated in
Fig. 4A. The experimental findings indicate that LiNixCoyMnzO2
Fig. 4 (A, a-spent LIBs, b–f-500 °C–700 °C) XRD pattern of roasted products and (B) LLi at various roasting temperatures with water leaching (roast-
ing time: 90 min, water leaching: 25 °C for 2 h, L/S = 10 mL g−1, 200 rpm stirring speed).
Fig. 5 SEM-EDS analysis of spent LIBs (a) and roasted products (b, 550 °C; c, 600 °C; d, 650 °C).
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was fully present when the roasting temperature was at 500 °C
and 550 °C, indicating incomplete dissociation and reduction
of LiNixCoyMnzO2 at 550 °C. At 600 °C, weak diffraction peaks
of LiNixCoyMnzO2 were still detectable, along with diffraction
peaks of Li2CO3, CoO, and MnO, which suggested that a
reduction reaction occurred within this temperature range.
However, LiNixCoyMnzO2 diffraction peaks were entirely
replaced by diffraction peaks of Li2CO3, metallic Ni, metallic Co,
and MnO at roasting temperatures of 650 °C and 700 °C.
Furthermore, a weak diffraction peak of LiAlO2 was observed in
the roasted products, resulting from the reaction between
Li2CO3 and Al under high-temperature conditions.20,33 This
reaction forms water-insoluble LiAlO2, reducing LLi, which is in
agreement with the experimental findings shown in Fig. 4B.
SEM-EDS analysis of mixed electrode materials and roasted
products is presented in Fig. 5 and Table 2. As the roasting
temperature increases to 650 °C (Fig. 5d), it becomes evident
that the agglomerated LiNixCoyMnzO2 material gradually
breaks down into small and irregular block particles. The
surface of these particles reveals uneven distribution of O, Ni,
Co, and Mn elements, indicating the complete destruction of
the cathode material’s crystal structure. Notably, the elemental
distribution shows enrichment areas for Ni, Co, and Mn, with
similar areas for Ni and Co. EDS analysis at a specific location
of the roasted products showed that point 2 had Mn and O
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Table 2 EDS elemental analysis of spent LIBs and roasted products temperature, while the binding energy peak belonging to
metallic Ni appeared at 852.6 eV.36 For the Co 2p energy spec-
Element (wt%) Point 1 Point 2 Point 3 Point 4 Point 5 trum in Fig. 6B, two binding energy peaks at 780.0 eV and
C 16.94 12.43 10.54 26.16 98.84 795.2 eV can be observed in the mixed electrode materials,
O 32.49 42.65 54.27 5.29 — indicating the presence of Co3+.37 For the roasted products,
Ni 25.30 — 21.66 68.56 —
Co 10.56 1.08 2.38 — 0.26 four main peaks of binding energy were observed at 781.2 eV,
Mn 13.67 42.85 10.60 — 0.19 797.3 eV, 778.1 eV, and 793.3 eV, which showed that Co3+ was
first reduced to Co2+ and finally reduced to metallic Co
through in situ thermal reduction.38 The Mn 2p energy spec-
trum (Fig. 6C) shows that Mn4+ (642.5 eV, 653.8 eV) in the
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contents exceeding 40 wt%, suggesting the presence of Mn

oxide in this region. Analysis of points 3 and 5 revealed incom-
plete reaction of smooth regular block particles with cathode
materials and graphite, respectively. Additionally, point 4
exhibited a Ni-rich phase (Ni > 48 wt%), which could be either
metallic Ni or NiO.
XPS analysis was conducted on mixed electrode materials
before and after in situ thermal reduction to further analyze
the products. The Ni 2p energy spectrum of these materials, as
depicted in Fig. 6A, the presence of binding energy peaks at
873.4 eV and 856.3 eV reveals the existence of Ni3+ states in the
Ni 2p1/2 and Ni 2p3/2 orbitals, respectively.34 A binding energy
peak observed at 854.6 eV confirms the presence of Ni2+.35
After in situ thermal reduction, the binding energy peaks
corresponding to Ni3+ disappeared with increasing roasting
mixed electrode materials is converted to Mn2+ (641.0 eV,
653.4 eV) during in situ thermal reduction.32 In the Li 1s
energy spectrum (Fig. 6D), 56.3 eV, 55.3 eV, and 54.9 eV corres-
pond to the oxidation state of Li+, Li2CO3, and LiAlO2, respect-
ively, as observed from apparent satellite features.39–41 The
XPS analysis results verified the XRD and SEM-EDS analysis.
The reasonable increase in roasting temperature facilitates Li
extraction. The optimal roasting temperature is 650 °C, and
the conventional water-leaching method resulted in a 77.96%
leaching efficiency of Li.
3.2.3. Effect of roasting time. The findings presented in
Fig. 7 demonstrate that after 30 min of roasting, a majority of
the LiNixCoyMnzO2 cathode material had dissociated into four
substances: Li2CO3, Ni, Co, and CoO. With an increase in

Fig. 6 XPS spectra of (A) Ni 2p, (B) Co 2p, (C) Mn 2p, and (D) Li 1s core peaks of the spent LIBs (a) and roasted products (b, 550 °C; c, 600 °C; d,
650 °C).

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Fig. 7 (A, a-spent LIBs, b–f-30 min–150 min) XRD pattern of roasted products and (B) LLi at various roasting temperatures with water leaching
(roasting temperature: 650 °C, water leaching: 25 °C for 2 h, L/S = 10 mL g−1, 200 rpm stirring speed).

roasting time to 60 min, there was a notable enhancement in
the diffraction peak intensity of Li2CO3, signifying a corres-
ponding increase in its content in the reduced products. This
in turn led to a significant improvement in the LLi. With a
further increase in roasting time, the intensity of the diffrac-
tion peaks corresponding to metallic Ni, metallic Co, and
MnO continued to increase, implying a more thorough
reduction reaction of the cathode material.42 Despite this
improvement, the emergence of LiAlO2 diffraction peaks led to
a gradual decrease in the LLi. Therefore, 60 min was selected
as the suitable roasting time under this research condition.
This optimal roasting time resulted in a higher LLi of 85.66%.
XPS was performed on mixed electrode materials and
roasted products of different roasting times, with a focus on
the Ni, Co, Mn, and Li elements as shown in Fig. 8. The
samples were labeled (a), (b), (c), and (d) to represent the

Fig. 8 XPS spectra of (A) Ni 2p, (B) Co 2p, (C) Mn 2p, and (D) Li 1s core peaks of the spent LIBs (a) and roasted products (b, 30 min; c, 60 min; d,
90 min).

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Green Chemistry
mixed electrode materials and the roasted products at 30, 60,
and 90 min, respectively. Fig. 8(a) displayed the valence state
analysis of the Ni element on the sample’s surface. As the
roasting time increased, the strength of the binding energy
peak of Ni3+ (873.4 eV and 856.3 eV) decreased continuously,
and the valence state of Ni was reduced from +3 to +2. At the
same time, a metallic Ni binding energy peak (852.6 eV) was
detected, indicating that some Ni3+ was reduced to metallic Ni
through an in situ reduction reaction.43 Fig. 8(b) shows a
narrow scan map of the Co element on the sample’s surface.
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The binding energy peak intensity of Co3+ at 780 eV and 795.2
eV continuously decreased with the extent of roasting time
from 30 min to 90 min, whereas the intensity of metallic Co at
778.1 eV and 793.3 eV significantly increased, indicating that
the reduction reaction of Co high-valent oxides became
increasingly complete. Fig. 8(c and d) highlights that when the
roasting time was 30 min, the high-valent oxide of Mn was
reduced to divalent manganese oxide, and the corresponding
Li2CO3 was generated. As the roasting time was extended to
60 min, the binding energy peak intensity of +2 valence Mn
and Li2CO3 enhanced, indicating that reduction roasting was
more sufficient and the amount of Li2CO3 was rising. However,
as the roasting time was further extended, a binding energy
peak belonging to lithium aluminate appeared at 54.9 eV,
which is not conducive to the leaching of lithium.
3.2.4. The phase evolution behavior of Li. The TOF-SIMS
spectrum ( positive ion) of the roasted products in Fig. 9(A)
shows that after the in situ reduction of mixed electrode
materials, the phases of Li present in the roasted products
include LiF, Li2CO3, Li2O, LiOH, and LiAlO2. This suggests that
the in situ reduction of the spent cathode material of
LiNixCoyMnzO2 is a result of the synergistic action of the
organic binder (PVDF), graphite, and aluminum foil at high
temperatures.44 Interestingly, a significant difference was
Fig. 9 (A) TOF-SIMS spectrum ( positive ion) and (B) ToF-SIMS image of the roasted products.
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observed between the ToF-SIMS images of LiF and Li2CO3
(Fig. 9B). This difference could be attributed to the organic
binder that was attached to the surface of some large cathode
material particles.45 During the process of in situ reduction
roasting, the organic binders were preferentially pyrolyzed
between 450–550 °C, leading to the formation of HF, pyrolytic
carbon, and various fluorobenzenes according to eqn (3).46 HF
gas has reduction properties that can reduce some of the
LiNixCoyMnzO2 to NiO, CoO, MnO, and LiF, as shown in eqn
(4). Pyrolysis residual carbon and graphite at 600–650 °C can
further reduce LiNixCoyMnzO2 to NiO, CoO, MnO, and Li2O.
Part of the Li2O can then react with CO2 to produce Li2CO3, as
demonstrated in eqn (5) and (6). Since the molar ratio of Li2O
to CO2 is 1 : 1, only a portion of Li2O reacts with CO2 during
this process, while the rest reacts with Al and H2O to form
LiAlO2 and LiOH. In general, the distribution of Li in the par-
ticles is relatively uniform and correlates with the distribution
of F and O. Additionally, the distribution of Li2CO3, Li2O,
LiAlO2, and LiOH is well-correlated.
–ðCF2 CH2 Þ-n ! HF þ C þ C6 H5 F ð3Þ
LiNi0:5 Co0:2 Mn0:3 O2 þ HF
ð4Þ
! F2 þ NiO þ CoO þ MnO þ LiF þ H2 O
15LiNi0:5 Co0:2 Mn0:3 O2 þ 3:25C ! 7:5Li2 O
ð5Þ
þ 7:5NiO þ Co3 O4 þ 4:5MnO þ 3:25CO2
Li2 O þ CO2 ! Li2 CO3 ð6Þ
3.3. Recovery of Li from roasted products
3.3.1. Ultrasonic-assisted water leaching. It is found that
the optimal LLi of 85.66% is obtained at optimum in situ
thermal reduction-water leaching conditions: roasting at
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650 °C for 60 min, water leaching at 25 °C for 2 h, L/S ratio of
15 : 1 (mL g−1), and 200 rpm stirring speed. To improve the LLi
and shorten the leaching time, ultrasonic is applied to the
water-leaching of roasted products. The results from the
experiment are presented in Fig. 10. It is observed that as the
ultrasonic power increased from 150 W to 450 W, the leaching
efficiency of Li steadily increased. However, the leaching
efficiency remained constant when the power was further
increased to 750 W (Fig. 10A). This can be attributed to the
fact that under the same frequency of the sound field and sur-
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rounding liquid environment, the intensity of ultrasonic power
determines the ultrasonic cavitation effect.25 Local cavitation
generated by ultrasonic waves in a solution medium can cause
the desorption of lithium ions adsorbed by carbon materials
into a liquid phase and promote the rapid dissolution of
Li2CO3.27 Therefore, to achieve the highest leaching efficiency
of Li, the ultrasonic power should be maintained at 450 W.
In Fig. 10B, the curves demonstrate the impact of ultrasonic
treatment on the LLi for different durations. Ultrasonic treat-
ment significantly enhanced the leaching efficiency of Li
within the 2–20 min range, with values ranging from 70.15%
to 93.59%. As the duration of ultrasonic treatment increased,
the LLi became more consistent. On the other hand, water
leaching at 25 °C for 2 h resulted in a lower leaching efficiency
of only 85.66%, indicating the superiority of the ultrasonic-
assisted water leaching method in terms of efficiency and time
consumption. The mechanical effects of ultrasound, such as
micro-jets and shock waves, produce microscopic turbulence
in the liquid and high-speed collisions between solids.47,48 As
a result, the solid surface undergoes constant erosion and par-
ticle destruction, leading to the acceleration of Li2CO3
diffusion and the generation of new reaction surfaces.
Traditional mechanical stirring leaching techniques struggle
to achieve this level of efficiency. Therefore, it can be inferred
that an ultrasonic treatment duration of 20 min is optimal for
achieving both economic and effective recovery of Li.
Fig. 10 LLi with the effect of different (A) ultrasonic power, (B) ultra-
sonic time, (C) L/S ratio, and (D) leaching temperature.
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Fig. 10C shows that the LLi exhibits a gradual increase with
an elevation in the L/S ratio, peaking at 98.30% when the L/S
ratio reaches 20 : 1 (mL g−1), and the efficiency remains
unchanged beyond this point. This suggests that, under
reasonable ultrasonic power and time, the liquid–solid ratio is
an important factor affecting LLi in the ultrasonic-assisted
water leaching process. The solubility of Li2CO3 is constant at
a given temperature. As such, a smaller liquid–solid ratio
results in a smaller mass of the soluble substance. Therefore,
the optimum L/S ratio is 20 : 1 (mL g−1).
It is widely recognized that a higher temperature leads to a
lower solubility of Li2CO3.29 However, within a specific range,
raising the temperature can enhance the kinetics of dis-
solution and thus promote the solubility of Li2CO3 in a water-
leaching solution.24 The optimal leaching efficiency for Li
(98.68%) was attained at 30 °C, and further elevation of the
leaching temperature did not contribute to the recovery of Li
(Fig. 10D). Therefore, from both economic and solubility
standpoints, 30 °C stands out as the optimal temperature
choice for the leaching process. In summary, the use of ultra-
sonic treatment during the water-leaching process can signifi-
cantly enhance the leaching efficiency of Li from roasted
products.
3.3.2. Ultrasonic enhanced leaching mechanism. Since
mixed electrode materials inevitably retain a significant quan-
tity of carbonaceous materials ( particularly anode graphite
materials) in the products of in situ reduction roasting, the car-
bonaceous materials can lead to two main challenges. First,
during the in situ reduction roasting process, LiF, Li2CO3,
Li2O, and LiOH can be covered by carbonaceous materials.
Secondly, carbonaceous materials can absorb lithium ions in
an aqueous solution, reducing the recovery rate of lithium.
The hexagonal structure of graphite crystals is covalently
bonded by carbon atoms, and the layers are bonded by weak
van der Waals forces. This unique structure allows lithium
ions to be embedded in the interlayer of graphite crystals
without damaging the two-dimensional network structure of
graphite.49 However, this process is reversible, as is the adsorp-
tion and desorption of lithium by graphite materials.
The addition of ultrasonic waves can effectively promote
the desorption of lithium from carbonaceous materials. The
leaching process is enhanced by ultrasound through the
mechanisms listed below: (a) the application of ultrasonic
waves can generate shock waves that induce the asymmetric
collapse on the surface and inside of the pores of the carbon-
aceous material, facilitating the desorption of the substance
from the solid surface and inside the pores. (b) By utilizing
ultrasonic waves, the interlayer structure of graphite crystals in
carbonaceous materials can be effectively destroyed. The asym-
metric collapse of cavitation bubbles generated by the ultra-
sonic waves causes a sudden change in temperature and
pressure that weakens the physical and chemical binding
between the lithium and the carbonaceous material, resulting
in improved Li recovery rates.50 (c) Ultrasonic waves can be
used to promote the desorption of lithium ions from carbon-
aceous materials by inducing micro-scale shock waves that
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create high-pressure regions within the material. This pressure

differential causes lithium ions to detach from the surface and
enter the surrounding solution (Fig. 11).
3.3.3. Recovery of lithium carbonate. After ultrasonic-
assisted water leaching, an excessively saturated Na2CO3 solu-
tion (1.2 times the theoretical amount) was slowly added to the
leaching solution. The recovered filtrate was evaporated and
crystallized at 95 °C, and Li2CO3 products were successfully
prepared. As shown in Fig. 12a, the resulting Li2CO3 product
was found to have well-crystallized particles, as confirmed by
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XRD analysis that matched the standard pattern peaks (JCPDS

no. 22-1441). Aqua regia was used to dissolve the Li2CO3
product, and the metal mass fraction was determined by
ICP-OES to ascertain its purity. The results showed that the
purity of the prepared Li2CO3 was 99.50%, with impurity con-
tents of Na < 0.135 wt%, S < 0.142 wt%, and others
<0.124 wt%, meeting the standard of battery-grade purity (YS/T Fig. 12 (a) XRD pattern and (b–d) SEM-EDS images of the prepared
582-2013). The results of microstructure analysis of the pre- Li2CO3 sample.

pared Li2CO3 showed that the particles were fine and distribu-
ted in block and bar-shaped clusters (Fig. 12b and c). The fine
particle size (about 1–10 μm) is beneficial for promoting inter-
facial reactions during cathode regeneration, which is impor-
tant for improving battery performance.51,52 Overall, the ultra-
sonic-assisted water leaching method was found to be an
effective and promising technique for producing high-purity
Li2CO3 for battery applications.
3.4. Wet magnetic separation-sulfuric acid leaching
After in situ thermal reduction, the magnetism of the roasted
products was found to be much higher than that of the unre-
duced mixed electrode materials, as evidenced by the hyster-
esis loop measured at room temperature (Fig. 13a). The satur-
ation magnetization of the roasted products was 9.42676 emu
g−1, compared to 1.82797 emu g−1 for the unreduced mixed
electrode materials (Fig. 13b). The improvement in magnetic
properties is crucial for facilitating the magnetic separation of
roasted products. Higher saturation magnetization means
higher magnetic properties, making it easier to separate the
products under the influence of an external magnetic field
with equal strength.53
Wet magnetic separation was employed to recover residual
high-value metals from the ultrasonic-assisted water leaching
residue. From Fig. 13(c–g), it can be observed that the concen-
trate obtained after magnetic separation contained Ni, NiO,
Co, and MnO, with SEM-EDS analysis confirming the partial
recovery of MnO through the reaction with metal Co and Ni to
form composite particles.22,54 The grey tailings are made up of
graphite, MnO, Al, Cu, and SiO2. One approach to recover
graphite from the grey tailings is through flotation separation,
while the remaining flotation tailings can be subjected to
gravity separation to recover Mn, Al, and Cu based on the
specific gravity difference of MnO, Al, and Cu. After low-inten-
sity wet magnetic separation, a Ni–Co–Mn-rich concentrate
with Co, Mn, and Ni grades of approximately 11.28 wt%,
16.03 wt%, and 23.89 wt%, respectively, and a total recovery of
86.36%, 59.10%, and 97.64% at a production yield of 47.22%
was obtained. The Co, Mn, and Ni were then recovered from
the Ni–Co–Mn-rich concentrate by sulphuric acid leaching
(acid concentration 3 M, S/L of 1 : 5 g mL−1, 30 °C for 2 h),
with final leaching efficiencies of 95.23%, 99.41%, and

Fig. 11 The mechanism of ultrasonic-assisted water leaching.

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Fig. 13 (a) The images and (b) the magnetic hysteresis curves of the
spent LIBs and roasting products, (c and d) the XRD patterns of the mag-
netic separation concentrate and tailings after wet magnetic separation,
(e) SEM-EDS images of the magnetic separation concentrate, (f ) the
metal grade and magnetic recovery efficiency of valuable metals, and (g)
the leaching efficiencies of Ni, Co, and Mn from magnetic separation
concentrate.
93.86%, respectively. The resulting filtrate was rich in high-
value metals (Co 18.77 g L−1, Mn 31.87 g L−1, Ni 44.86 g L−1),
which could then undergo further treatment using various sep-
aration technologies such as precipitation.55
4. Conclusion
This study proposes a novel approach for maximizing the step-
wise selective recovery of valuable metals from mixed electrode
materials in spent LIBs without the need for pre-sorting. The
complete maximum selectivity recovery process fully utilizes
the valuable components of mixed electrode materials from
spent LIBs, reduces secondary pollution caused by repeated
purification, and effectively recovers precious metals.
1 The thermodynamic calculations and microstructural
analyses indicate that the mixed electrode material was pri-
marily transformed into Li2CO3, Ni, Co, NiO, and MnO under
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the optimal roasting conditions of 650 °C for 60 min. The
maximum leaching efficiency of Li under conventional water-
leaching conditions was found to be 85.66%. However, increas-
ing the roasting temperature or prolonging the roasting time
under optimal roasting conditions resulted in the conversion
of Li into insoluble LiAlO2, which decreased the leaching
efficiency of Li. TOF-SIMS spectra ( positive ions) of the roasted
products showed that during the in situ reduction of mixed
electrode materials, the spent cathode material LiNixCoyMnzO2
underwent in situ reduction due to the synergic action of the
organic binder (PVDF), graphite and aluminum foil at high
temperature. The phases of Li present in the roasted products
include LiF, Li2CO3, Li2O, LiOH, and LiAlO2.
2 The effects of ultrasound cavitation induced by soni-
cation, increased the Li leaching efficiency to 98.68% (more
than a 13% increase), attributed to several effects: first, it
induces asymmetric collapse on the surface and inside of the
pores of carbonaceous material, facilitating substance desorp-
tion. Second, it destroys the interlayer structure of graphite
crystals, weakening the binding between lithium and carbon-
aceous material, resulting in improved Li recovery rates. Third,
it creates micro-scale shock waves that induce high-pressure
regions, promoting lithium ion desorption from carbonaceous
materials.
3 High-purity Li2CO3 (99.50%) was obtained by evaporative
crystallization of the recovered lixivium. Subsequently, the
transition metals were separated from aluminum, copper, and
graphite by wet magnetic separation. Over 93% of high-value
metals Ni, Mn, and Co in the magnetically enriched products
were leached by sulfuric acid at room temperature without a
reducing agent, which greatly simplified the subsequent tran-
sition metal separation process.
The developed method demonstrates its flexibility in reco-
vering spent LIBs as it is performed on mixed electrode
materials that are not pre-sorting, which is representative of
the reality of industrial recycling facilities. Additionally, no
chemical-reducing agent is added to the treatment process,
making it a self-sustaining and environmentally friendly
process. However, the entire recycling process requires mul-
tiple steps, each involving different operations and equipment,
and therefore requires corresponding facilities and technical
support, which may increase operational complexity and pro-
duction investment costs. Overall, this work opens up a new
idea and method for the efficient and selective stepwise clean
extraction of valuable metals from the mixed electrode
materials of spent LIBs without pre-sorting.
Author contributions
Wei Ding: methodology, experimental design and data collec-
tion, investigation, draft writing and editing. Shenxu Bao: con-
ceptualization, funding acquisition, project administration,
revised the manuscript. Yiming Zhang, Liuyi Ren: supervision,
Chunfu Xin, Bo Liu: investigation. Bo Chen, Junhui Xiao:
review & editing.
This journal is © The Royal Society of Chemistry 2023

Green Chemistry
Conflicts of interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
This research was supported by the Key R&D Program of
Published on 02 August 2023. Downloaded by Universitas Indonesia on 8/19/2023 4:37:44 AM.
Zhejiang Province, China (2022C03061), the National Natural
Science Foundation of China (52074204), and the
Fundamental Research Funds for the Central Universities
(2023-vb-032).
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